Beyond the Born-Oppenheimer approximation: high-resolution overtone spectroscopy of H2D+ and D2H+

Transitions to overtone 2v2 and 2v3, and combination v2 + v3 vibrations in jet-cooled H2D+ and D2H+ molecular ions have been measured for the first time by high-resolution IR spectroscopy. The source of these ions is a pulsed slit jet supersonic discharge, which allows for efficient generation, rotational cooling, and high frequency (100 KHz) concentration modulation for detection via sensitive lock-in detection methods. Isotopic substitution and high-resolution overtone spectroscopy in this fundamental molecular ion permit a systematic, first principles investigation of Born–Oppenheimer "breakdown" effects due to large amplitude vibrational motion as well as provide rigorous tests of approximate theoretical methods beyond the Born–Oppenheimer level. The observed overtone transitions are in remarkably good agreement (<0.1 cm–1) with non-Born–Oppenheimer ab initio theoretical predictions, with small but systematic deviations for 2v2, 2v + 3v, and 2v3 excited states indicating directions for further improvement in such treatments. Spectroscopic assignment and analysis of the isotopomeric transitions reveals strong Coriolis mixing between near resonant 2v3 and 2v + 3v vibrations in D2H+. Population-independent line intensity ratios for transitions from common lower states indicate excellent overall agreement with theoretical predictions for D2H+, but with statistically significant discrepancies noted for H2D+. Finally, H2D+ versus D2H+ isotopomer populations are analyzed as a function of D2/H2 mixing ratio and can be well described by steady state kinetics in the slit discharge expansion

Generation and orientation of organoxenon molecule H–Xe–CCH in the gas phase

We report on the first observation of the organoxenon HXeCCH molecule in the gas phase. This molecule has been prepared in a molecular beam experiment by 193 nm photolysis of an acetylene molecule on Xen clusters (¯n ≈ 390). Subsequently the molecule has been oriented via the pseudofirst-order Stark effect in a strong electric field of the polarized laser light combined with the weak electrostatic field in the extraction region of a time-of-flight spectrometer. The experimental evidence for the oriented molecule has been provided by measurements of its photodissociation. For comparison, photolysis of C₂H₂ on Arn clusters (¯n ≈ 280) has been measured. Here the analogous rare gas molecule HArCCH could not be generated. The interpretation of our experimental findings has been supported by ab initio calculations. In addition, the experiment together with the calculations reveals information on the photochemistry of the HXeCCH molecule. The 193 nm radiation excites the molecule predominantly into the 2¹∑⁺ state, which cannot dissociate the Xe-H bond directly, but the system evolves along the Xe-C coordinate to a conical intersection of a slightly non-linear configuration with the dissociative 1¹∏ state, which then dissociates the Xe-H bond

Observations of conduction driven evaporation in the early rise phase of solar flares

&lt;p&gt;&lt;b&gt;Context:&lt;/b&gt; The classical flare picture features a beam of electrons, which were accelerated in a site in the corona, hitting the chromosphere. The electrons are stopped in the dense chromospheric plasma, emitting bremsstrahlung in hard X-rays. The ambient material is heated by the deposited energy and expands into the magnetic flare loops, a process termed chromospheric evaporation. In this view hard X-ray emission from the chromosphere is succeeded by soft-X-ray emission from the hot plasma in the flare loop, the soft X-ray emission being a direct consequence of the impact of the non-thermal particle beam. However, observations of events exist in which a pronounced increase in soft X-ray emission is observed minutes before the onset of the hard X-ray emission. Such pre-flare emission clearly contradicts the classical flare picture.&lt;/p&gt; &lt;p&gt;&lt;b&gt;Aims:&lt;/b&gt; For the first time, the pre-flare phase of such solar flares is studied in detail. The aim is to understand the early rise phase of these events. We want to explain the time evolution of the observed emission by means of alternative energy transport mechanisms such as heat conduction.&lt;/p&gt; &lt;p&gt;&lt;b&gt;Methods:&lt;/b&gt; RHESSI events displaying pronounced pre-flare emission were analyzed in imaging and spectroscopy. The time evolution of images and full sun spectra was investigated and compared to the theoretical expectations from conduction driven chromospheric evaporation. Results. The pre-flare phase is characterized by purely thermal emission from a coronal source with increasing emission measure and density. After this earliest phase, a small non-thermal tail to higher energies appears in the spectra, becoming more and more pronounced. However, images still only display one X-ray source, implying that this non-thermal emission is coronal. The increase of emission measure and density indicates that material is added to the coronal region. The most plausible origin is evaporated material from the chromosphere. Energy provided by a heat flux is capable of driving chromospheric evaporation. We show that the often used classical Spitzer treatment of the conductive flux is not applicable. The conductive flux is saturated. During the preflare-phase, the temperature of the coronal source remains constant or increases. Continuous heating in the corona is necessary to explain this observation.&lt;/p&gt; &lt;p&gt;&lt;b&gt;Conclusions:&lt;/b&gt; The observations of the pre-flare phase of four solar flares are consistent with chromospheric evaporation driven by a saturated heat flux. Additionally, continuous heating in the corona is necessary to sustain the observed temperature.&lt;/p&gt

Ring formation and hydration effects in electron attachment to misonidazole

This research was funded by CZECH SCIENCE FOUNDATION grant number 19-01159S; Czech Ministry of Education Youth and Sports via OP RDE Grant no. CZ.02.2.69/0.0/16_027/0008355; S.D. acknowledges funding from the FWF, Vienna (P30332).We study the reactivity of misonidazole with low-energy electrons in a water environment combining experiment and theoretical modelling. The environment is modelled by sequential hydration of misonidazole clusters in vacuum. The well-defined experimental conditions enable computational modeling of the observed reactions. While the NO- 2 dissociative electron attachment channel is suppressed, as also observed previously for other molecules, the OH- channel remains open. Such behavior is enabled by the high hydration energy of OH- and ring formation in the neutral radical co-fragment. These observations help to understand the mechanism of bio-reductive drug action. Electron-induced formation of covalent bonds is then important not only for biological processes but may find applications also in technology.publishersversionpublishe

Temporal Correlation of Hard X-rays and Meter/Decimeter Radio Structures in Solar Flares

We investigate the relative timing between hard X-ray (HXR) peaks and structures in metric and decimetric radio emissions of solar flares using data from the RHESSI and Phoenix-2 instruments. The radio events under consideration are predominantly classified as type III bursts, decimetric pulsations and patches. The RHESSI data are demodulated using special techniques appropriate for a Phoenix-2 temporal resolution of 0.1s. The absolute timing accuracy of the two instruments is found to be about 170 ms, and much better on the average. It is found that type III radio groups often coincide with enhanced HXR emission, but only a relatively small fraction ($\sim$ 20%) of the groups show close correlation on time scales $<$ 1s. If structures correlate, the HXRs precede the type III emissions in a majority of cases, and by 0.69$\pm$0.19 s on the average. Reversed drift type III bursts are also delayed, but high-frequency and harmonic emission is retarded less. The decimetric pulsations and patches (DCIM) have a larger scatter of delays, but do not have a statistically significant sign or an average different from zero. The time delay does not show a center-to-limb variation excluding simple propagation effects. The delay by scattering near the source region is suggested to be the most efficient process on the average for delaying type III radio emission

Survey on solar X-ray flares and associated coherent radio emissions

The radio emission during 201 X-ray selected solar flares was surveyed from 100 MHz to 4 GHz with the Phoenix-2 spectrometer of ETH Zurich. The selection includes all RHESSI flares larger than C5.0 jointly observed from launch until June 30, 2003. Detailed association rates of radio emission during X-ray flares are reported. In the decimeter wavelength range, type III bursts and the genuinely decimetric emissions (pulsations, continua, and narrowband spikes) were found equally frequently. Both occur predominantly in the peak phase of hard X-ray (HXR) emission, but are less in tune with HXRs than the high-frequency continuum exceeding 4 GHz, attributed to gyrosynchrotron radiation. In 10% of the HXR flares, an intense radiation of the above genuine decimetric types followed in the decay phase or later. Classic meter-wave type III bursts are associated in 33% of all HXR flares, but only in 4% they are the exclusive radio emission. Noise storms were the only radio emission in 5% of the HXR flares, some of them with extended duration. Despite the spatial association (same active region), the noise storm variations are found to be only loosely correlated in time with the X-ray flux. In a surprising 17% of the HXR flares, no coherent radio emission was found in the extremely broad band surveyed. The association but loose correlation between HXR and coherent radio emission is interpreted by multiple reconnection sites connected by common field lines.Comment: Solar Physics, in pres

Multi-wavelength analysis of high energy electrons in solar flares: a case study of August 20, 2002 flare

A multi-wavelength spatial and temporal analysis of solar high energy electrons is conducted using the August 20, 2002 flare of an unusually flat (gamma=1.8) hard X-ray spectrum. The flare is studied using RHESSI, Halpha, radio, TRACE, and MDI observations with advanced methods and techniques never previously applied in the solar flare context. A new method to account for X-ray Compton backscattering in the photosphere (photospheric albedo) has been used to deduce the primary X-ray flare spectra. The mean electron flux distribution has been analysed using both forward fitting and model independent inversion methods of spectral analysis. We show that the contribution of the photospheric albedo to the photon spectrum modifies the calculated mean electron flux distribution, mainly at energies below 100 keV. The positions of the Halpha emission and hard X-ray sources with respect to the current-free extrapolation of the MDI photospheric magnetic field and the characteristics of the radio emission provide evidence of the closed geometry of the magnetic field structure and the flare process in low altitude magnetic loops. In agreement with the predictions of some solar flare models, the hard X-ray sources are located on the external edges of the Halpha emission and show chromospheric plasma heated by the non-thermal electrons. The fast changes of Halpha intensities are located not only inside the hard X-ray sources, as expected if they are the signatures of the chromospheric response to the electron bombardment, but also away from them.Comment: 26 pages, 9 figures, accepted to Solar Physic

Diagnostics of non-thermal distributions in solar flare spectra observed by RESIK and RHESSI

We focus on the non-thermal components of the electron distribution in the keV range and analyse high-energy resolution X-ray spectra detected by RESIK and RHESSI for three solar flares.In the 2-4 keV range we assume that the electron distribution can be modelled by an n-distribution. Using a method of line-intensity ratios, we analyse allowed and satellite lines of Si observed by RESIK and estimate the parameters of this n-distribution. At higher energies we explore RHESSI bremsstrahlung spectra. Adopting a forward-fitting approach and thick-target approximation, we determine the characteristics of injected electron beams. RHESSI non-thermal component associated with the electron beam is correlated well with presence of the non-thermal n-distribution obtained from the RESIK spectra. In addition, such an n-distribution occurs during radio bursts observed in the 0.61-15.4 GHz range. Furthermore, we show that the n-distribution could also explain RHESSI emission below ~5 keV. Therefore, two independent diagnostics methods indicate the flare plasma being affected by the electron beam can have a non-thermal component in the ~2-5 keV range, which is described by the n-distribution well. Finally, spectral line analysis reveals that the n-distribution does not occupy the same location as the thermal component detected by RHESSI at ~10 keV.Comment: 18 pages, 14 figures, 10 table

An Observational Overview of Solar Flares

We present an overview of solar flares and associated phenomena, drawing upon a wide range of observational data primarily from the RHESSI era. Following an introductory discussion and overview of the status of observational capabilities, the article is split into topical sections which deal with different areas of flare phenomena (footpoints and ribbons, coronal sources, relationship to coronal mass ejections) and their interconnections. We also discuss flare soft X-ray spectroscopy and the energetics of the process. The emphasis is to describe the observations from multiple points of view, while bearing in mind the models that link them to each other and to theory. The present theoretical and observational understanding of solar flares is far from complete, so we conclude with a brief discussion of models, and a list of missing but important observations.Comment: This is an article for a monograph on the physics of solar flares, inspired by RHESSI observations. The individual articles are to appear in Space Science Reviews (2011